Syntheses And Structures Of D~0-Early Transition-metal Amide Complexes

The development of new high dielectric constant (high-k) material, which is used to replace silicon dioxide as gate material, is one of the biggest technical challenges in the field of microelectronic materials in the nano era. The CVD reactions of metal alkoxides, silicides and amides complexes have been used for preparation of these materials. However, the molecular pathways of CVD reactions are still not clear since the process of CVD reaction is complicated. Designing and preparing the transiton metal alkoxides, silicides and amides complexes which can be used as CVD precursors, and the studies of the relationship of the composition and the structure of transition metal complexes and formation of high-k film materials will provide theoretical support for screening and synthesis of potential high-k materials.We prepared some transition metal d0-amide complexes, which can be used as CVD precursors, by the reactions of transition metal chlorides (TaCls, NbCls, ZrCl4, HfCl4) with bis(trimethylsily)amido lithium [LiN(SiMe3)2], dimethylamido lithium (LiNMe2) and CyN=C=NCy. The characterizations were confirmed by NMR, single-crystal X-ray diffraction.1.Reaction of TaCls, NbCls with bis(trimethylsily)amido lithium LiN(SiMe3)2afforded TaCl3[N(SiMe3)2]2(1), NbO[N(SiMe3)2]3(2), and exploring the reaction of TaCl3[N(SiMe3)2]2(1) with LiNMe2by NMR.2. Reaction of ZrCl4, HfCl4with bis(trimethylsily)amido lithium LiN(SiMe3)2afforded ZrCl[N(SiMe3)2]3(3), HfCl[N(SiMe3)2]3(4), and exploring the reaction of ZrCl[N(SiMe3)2]3(3), HfCl[N(SiMe3)2]3(4) with H3SiPh, LiNMe2by NMR respectively.3. Exploring the reaction of TaCl5with MCyN(N(SiMe3)2NCy(M=Li, K) in a1:1molar ratio.